1-Butenoyl-3,3-dimethylcyclohexane mixtures

ABSTRACT

1-BUTENOYL-3,3-DIMETHYLCYCLOHEXANE MIXTURES HAVING A SWEET ROOTBEER-LIKE, CEDARWOOD FLAVOR USEFUL AS FLAVORANTS IN FOODSTUFFS ARE DESCRIBED.

This application is a divisional of application for United States LetterPatent, Ser. No. 740,948, filed on Nov. 11, 1976, now U.S. Pat. No.4,081,481, which, in turn, is a continuation-in-part of U.S. applicationfor Letters Patent, Ser. No. 713,357, filed on Aug. 11, 1976, now U.S.Pat. No. 4,062,894, issued on Dec. 13, 1977.

BACKGROUND OF THE INVENTION

The present invention relates to 1-butanoyl-3,3-dimethylcyclohexanehaving the structure: ##STR1## AND NOVEL COMPOSITIONS USING SUCH1-BUTANOYL-3,3-DIMETHYLCYCLOHEXANES TO AUGMENT OR ENHANCE THE AROMA OFPERFUME COMPOSITIONS, COLOGNES AND PERFUMED ARTICLES.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various perfume compositions, perfumed articles and colognes. Thesesubstances are used to diminish the use of natural materials, some ofwhich may be in short supply and to provide more uniform properties inthe finished product.

Fruity, berry, herbaceous aromas with green and tobacco nuances aredesirable in several types of perfume compositions, perfumed articlesand colognes.

Acetylcyclohexane and 1-acetyl-3,3-dimethylcyclohexane are knownsubstituents in perfumery. Thus, Arctander, "Perfume and FlavorChemicals (Aroma Chemicals)," published in 1969, disclosesacetylcyclohexane in Volume I, number 36:

"Peculiar camphoraceous-sweet odor with a certain amount of floraltones.

Although this chemical would primarily lend itself to perfumecompositions in the Pine, Wood, Herbaceous and other non-floral types,it has a similarity to the harsh-floral types such as Hyacinth, etc. andits sweetness is sometimes classified as `musky.`"

1-Acetyl-3,3-dimethylcyclohexane is disclosed as a fragrance material inU.S. Pat. No. 3,487,102 issued on Dec. 30, 1969.

The fragrance properties of the aforementioned acetyldimethylcyclohexanederivatives are different in kind from the fragrance properties of thecompound of the instant invention.

Firmenich's Dutch published application 7500838 discloses thepreparation of the compound having the structure: ##STR2## and disclosesits use in perfumery and in augmenting foodstuff flavors. The perfumeryuse of this compound and other members of its class as "floral, green,herbaceous and chypre" useful in galbanum resinoids is also disclosed.

The compounds disclosed in Dutch published application 7500838 haveorganoleptic properties which cause them to be different in kind fromthe 1-butanoyl-3,3-dimethylcyclohexane of our invention, which hasunobvious, unexpected and advantageous characteristics in the field ofaugmenting or enhancing the organoleptic impressions of perfumes,colognes and perfumed articles.

THE INVENTION

It has now been discovered that novel perfume compositions, colognes andperfumed articles having fruity, berry, hergaceous aromas with green andtobacco nuances may be provided by the utilization of1-butanoyl-3,3-dimethylcyclohexane having the formula: ##STR3##

The 1-butanoyl-3,3-dimethylcyclohexane useful as indicated supra may beproduced preferably by a process which comprises the reaction of1-acetyl-3,3-dimethylcyclohexane with acetaldehyde in the presence of aninorganic base or a mixture of boron oxide (B₂ O₃) and boric acid,thereby producing a compound having the structure: ##STR4## (mixture of"cis" and "trans" isomers) and a compound having the structure: ##STR5##and then reducing the resulting product with hydrogen thereby producinga compound having the structure: ##STR6##

The first reaction with acetaldehyde is carried out at a temperature offrom about 20° C. up to 160° C., when using a catalyst which is aninorganic base, such as an alkali metal hydroxide, for example,potassium hydroxide, sodium hydroxide and lithium hydroxide or analkaline earth metal hydroxide such as barium hydroxide or lithiumhydroxide; or at a temperature in the range of from about 100° C. up to200° C. when using a catalyst which is a mixture of boric acid (HBO₃)and boron oxide.

The time of reaction is inversely proportional to the temperature ofreaction. Thus, when using a mixture of boric acid and boron oxide thetime of reaction varies between 2 and 10 hours and when using a highertemperature, the time of reaction varies from between 1 and 8 hours.

When using an inorganic base, the mole ratio of inorganicbase:1-acetyl-3,3-dimethylcyclohexane may vary from 0.1:1 up to 2:1 witha mole ratio of 1:1 being preferred. When using the mixture of boricacid and boron oxide, the mole ratio of boronoxide:1-acetyl-3,3-dimethylcyclohexane varies from 0.5:1 up to 1.5:1with a mole ratio of 1:1 being preferred. The concentration of boricacid in the reaction mass may vary from 1 up to 80 grams per mole ofacetaldehyde.

In all cases the mole ratio ofacetaldehyde:1-acetyl-3,3-dimethylcyclohexane may vary from 1:1 up toabout 3:1 with a mole ratio of 2:1 being preferred.

The reactions may take place in the presence or in the absence of aninert solvent. When using boric acid or boric oxide, the reactionpreferably is carried out without solvent. When using an inorganic basecatalyst, the reaction preferably takes place using a solvent such asmethanol, ethanol or isopropanol.

The reduction reaction to form the compound having the structure:##STR7## is carried out preferably in the presence of inert solventssuch as isopropyl alcohol; at hydrogenation pressures of between 50 and15- psig; at temperatures of between 25° and 150° C., and usinghydrogenation catalysts such as 5% palladium-on-carbon, rhodium,platinum and Raney nickel. The time of reaction varies inversely withthe temperature and pressure of reaction. Thus, lower pressures andtemperatures give rise to a need for greater times of reaction. Thus,the time of reaction may vary from 1 hour up to 5 hours.

The previous reaction sequence is illustrated as follows: ##STR8##wherein one of the dashed lines represents a carbon-carbon double bondand the other of the dashed lines represents a carbon-carbon singlebond.

The 1-butanoyl-3,3-dimethylcyclohexane of our invention and one or moreauxiliary perfume ingredients, including, for example, alcohols,aldehydes, nitriles, esters, cyclic esters (or lactones) and naturalessential oils, may be admixed so that the combined odors of theindividual components produce a pleasant and desired fragrance,particularly and preferably in amber fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low-boiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics; however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingreduents. Thus, the1-butanoyl-3,3-dimethylcyclohexene can be used to alter, modify orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of 1-butanoyl-3,3-dimethylcyclohexane of our invention whichwill be effective in perfume compositions as well as in perfumedarticles and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% of a1-butanoyl-3,3-dimethylcyclohexane or even less (e.g., 0.005%) can beused to impart a fruity, berry, herbaceous aroma with green and tobacconuances to soaps, cosmetics or other products. The amount employed canrange up to 70% of the fragrance components and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The 1-butanoyl-3,3-dimethylcyclohexane of our invention is useful [takenalone or together with other ingredients in perfume compositions] as anolfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, fact powders and the like. When used as anolfactory component as little as 1% of the1-butanoyl-3,3-dimethylcyclohexane will suffice to impart an intenseherbaceous note to amber formulations. Generally no more than 3% of the1-butanoyl-3,3-dimethylcyclohexane based on the ultimate end product isrequired in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the1-butanoyl-3,3-dimethylcyclohexane. The vehicle can be a liquid such asa non-toxic alcohol, a non-toxic glycol, or the like. The carrier canalso be an absorbent solid such as a gum (e.g., gum arabic) orcomponents for encapsulating the composition (such as gelatin).

It will thus be apparent that the 1-butanoyl-3,3-dimethylcyclohexane ofour invention can be utilized to alter, modify or enhance fragrances ofa wide variety of consumable materials.

The following examples serve to illustrate our invention, and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I SYNTHESIS OF 1-(3,3-DIMETHYLCYCLOHEXYL)-CIS and TRANS-(2 and3)-BUTEN-1-ONE

Reaction: ##STR9##

A mixture of 616 grams of 1-acetyl-3,3-dimethylcyclohexane (4 moles),132 grams of acetaldehyde (3 moles), 105 grams boron oxide (1.5 moles)and 12 grams of boric acid (0.2 moles) is heated at 150° C. in anautoclave for 3 hours. After cooling to room temperature the solution isfiltered from inorganic salts, washed once with aqueous sodium carbonateand twice with saturated salt solution. Distillation through a shortcolumn afforded 127.2 grams of 1-acetyl-3,3-dimethylcyclohexane and127.2 grams of a mixture of 1-(3,3-dimethylcyclohexyl)-cis andtrans-2-buten-1-one and 1-(3,3-dimethylcyclohexyl)-3-buten-1-one.

A portion of the distillate rich in the desired product(s) was distilledthrough a 1" × 12" Goodloe column giving the following fractions:

    ______________________________________                                                Vapor    Liquid                                                       Fraction                                                                              Temp.    Temp.    Vacuum  Weight Reflux                               No.     (° C.)                                                                          (° C.)                                                                          (mm Hg) (g)    Ratio                                ______________________________________                                        1       67-70    89-91    4.4-4.7 37.9   2:1                                  2        70       95      4.9     40.9   2:1                                  3        70      103      5.0     40.1   2:1                                  4        74      113      5.0     29.9   2:1                                  5       100      116      5.4     16.7   9:1                                  6       102      123      4.8     17.1   9:1                                  7       102      125      5.0     29.2   9:1                                  8       112      131      8.2     20.7   9:1                                  9       106      139      5.7     22.8   9:1                                  10      104      154      5.2     13.3   9:1                                  11      104      179      5.3     11.3   9:1                                  12      100      202      5.2      6.7   9:1                                  ______________________________________                                    

Bulked fractions 6-10 at 2 ppm, have a cedarwood aroma and a sweet,rootbeer-like, cedarwood flavor.

The mass spectral analysis is as follows:

180/69, 41, 39, 55, 165, 27.

The NMR analysis is as follows:

    ______________________________________                                        0.94 ppm (s)   gem dimethyl protons                                                                           6 H                                           1.74- 1.08 (m)                                                                                ##STR10##       8 H                                           1.90 (doublet with allylic coupling)                                                          ##STR11##       3 H                                           2.74 (m)                                                                                      ##STR12##       1 H                                           6.18 (broad doublet)                                                                          ##STR13##       1 H                                           7.04- 6.70 (m)                                                                                ##STR14##       1 H                                           ______________________________________                                    

the IR analysis is as follows:

960 cm⁻¹, 1290, 1360, 1380, 1440, 1625, 1670, 1690, 2860, 2940.

EXAMPLE II HYDROGENATION OF 1-(3,3-DIMETHYLCYCLOHEXYL)-CIS AND TRANS-(2and 3)-BUTEN-1-ONE

Reaction: ##STR15##

Into a 250 cc Parr shaker is placed 107 grams (6 moles) of1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-buten-1-one preparedaccording to Example I, 1 gram of 5% Palladium-on-carbon catalyst and125 grams of isopropyl alcohol. The Parr shaker is sealed and heated toa temperature of 125° C. at a pressure of 50-150 psig of hydrogen andmaintained at that pressure range and temperature range for a period of1.5 hours. At the end of the 1.5 hour period the reaction product isfiltered, the solvent is removed in vacuo, and the residual oil isdistilled on a 8 plate Vigreaux column. The distillation data follows:

    ______________________________________                                                Vapor    Liquid                                                       Fraction                                                                              Temp.    Temp.    Vacuum  Weight Reflux                               No.     (° C.)                                                                          (° C.)                                                                          (mm Hg) (g)    Ratio                                ______________________________________                                        1       86-89    100      4.6     9.0    11:1                                 2       90       102      4.7     12.0   11:1                                 3       90       102      4.6     8.8    11:1                                 4       90       102      4.7     11.5   11:1                                 5       90       105      4.6     14.0   11:1                                 6       90       110      4.6     13.5   11:1                                 7       90       113      4.6     8.4    11:1                                 8       90       141      4.6     11.1   11:1                                 9       90       205      4.6     4.4    11:1                                 ______________________________________                                    

From a perfumery standpoint fraction 7 at 10% in food grade alcohol hasa fruity, berry, herbaceous aroma with green, tobacco nuances.

The mass spectral analysis is as follows:

182/111, 69, 43, 41, 71, 55, 27.

The NMR analysis is as follows (fraction 8):

    ______________________________________                                        0.90 ppm (t)      CH.sub.3CH.sub.2   3 H                                      0.91 ppm (s)      dimethyl protons   6 H                                      1.95 - 1.16                                                                            (m)      CH.sub.2          10 H                                      2.49     (t)                                                                                     ##STR16##         2 H                                      2.69 - 2.31                                                                            (m)                                                                                     ##STR17##         1H                                       ______________________________________                                    

the IR analysis (fraction 8) is as follows:

1020 cm⁻¹, 1120, 1175, 1290, 1360, 1375, 1400, 1455, 1705, 2860, 2930.

EXAMPLE III

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient            Amount (Grams)                                          ______________________________________                                        n-Decyl Aldehyde      1                                                       n-Dodecyl Aldehyde    2                                                       Methyl Nonyl Acetaldehyde                                                                           0.5                                                     Linalool              50                                                      Linalyl Acetate       70                                                      Phenyl Ethyl Alcohol  100                                                     Petigrain SA          20                                                      Bergamot Oil          30                                                      Alpha Methyl Ionone   25                                                      1-(3,3-dimethylcyclohexyl)-                                                   butan-1-one produced according                                                to Example II         10                                                      Cyclized Bicyclo C-12 material                                                produced according to the process                                             of Example IV of Canadian Patent                                              854,225 issued on October 20, 1970                                                                  5                                                       Isobornyl Cyclohexyl Alcohol                                                                        10                                                      Benzyl Acetate        25                                                      2-n-Heptylcyclopentanone                                                                            5                                                                             353.3 (TOTAL)                                           ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel natural amber quality. This basecomposition can be admixed with aqueous ethanol, chilled and filtered toproduce a finished cologne. The cologne so prepared has an amber aromaleaning towards a woody amber note with excellent fruity and herbacenousnuances. The base composition can also be used to scent soap or othertoilet goods such as lotion, aerosol, sprays and the like.

EXAMPLE IV PREPARATION OF A COSMETIC-POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of 1-(3,3-dimethylcyclohexyl)-butan-1-one preparedaccording to Example II. It has an excellent fruity, berry, herbaceousaroma with green and tobacco nuances.

EXAMPLE V PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl-benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818issued on Apr. 6, 1976) with a herbaceous odor are prepared containing0.10%, 0.15% and 0.20% of 1-(3,3-dimethylcyclohexyl)-butan-1-oneprepared according to Example II. They are prepared by adding andhomogeneously mixing the appropriate quantity of1-(3,3-dimethylcyclohexyl)-butan-1-one in the liquid detergent. Thedetergents all possess a herbaceous fragrance with green and tobacconuances, the intensity increasing with greater concentrations of1-(3,3-dimethylcyclohexyl)-butan-1-one.

EXAMPLE VI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

1-(3,3-Dimethylcyclohexyl)-butan-1-one prepared according to the processof Example II is incorporated in a cologne at a concentration of 2.5% in85% aqueous ethanol; and into a handkerchief perfume at a concentrationof 20% (in 95% aqueous ethanol). A distinct and definite herbaceousfragrance is imparted to the cologne and to the handkerchief perfume.

EXAMPLE VII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition of Example III is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use of1-(3,3-dimethylcyclohexyl)-butan-1-one in the composition of Example IIIaffords a distinct and definite strong amber aroma with herbaceous andtobacco notes to the handkerchief perfume and cologne.

EXAMPLE VIII PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram of1-(3,3-dimethylcyclohexyl)-butan-1-one of Example II until asubstantially homogeneous composition is obtained. The perfumed soapcomposition manifests an excellent fruity, berry, tobacco aroma withgreen and tobacco nuances.

EXAMPLE IX PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder (Lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818issued Apr. 6, 1976) is mixed with 0.15 g of the1-(3,3-dimethylcyclohexyl)-butan-1-one of Example II until asubstantially homogeneous composition is obtained. This composition hasan excellent fruity, berry, herbaceous aroma with green and tobacconuances.

What is claimed is:
 1. A mixture of 1-butenoyl-3,3-dimethylcyclohexanesrepresented by the structure: ##STR18## wherein said mixture consists ofcompounds having the structure: ##STR19## and wherein one of the dashedlines represents a carbon-carbon single bond and the other of the dashedlines represents a carbon-carbon double bond.